Oxygen → HCID 607197, compound

HRID 612743Notes

Reaction equation

HRID 612743 reaction equation
[CH2:1]([N:3]([CH2:10][C:11]#[CH:12])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)[CH3:2].O=O>CN(C)C=O.Cl[Cu]>[CH2:1]([N:3]([CH2:10][C:11]#[C:12][C:12]#[C:11][CH2:10][N:3]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)[CH2:1][CH3:2])[C:4]1[CH:5]=[CH:6][CH:7]=[CH:8][CH:9]=1)[CH3:2]

Participants

5

Reactant 2

HCID 977OxygenHCID 3683082Benzenamine, N-ethyl-N-2-propynyl-

Product 1

HCID 607197HCID 607197, compoundYield 62%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 6228DimethylformamideSolvent2×

Procedure

The procedure follows that of Schlier (Ph.D. Thesis, Universitat Freiburg (1980)). To a stirred mixture of CuCl (4.90 g, 0.0495 Moles) in 300 mL Dimethylformamide (DMF) at room temperature in a bubbler was added N,N,N,N-Tetramethylenediamine (5.54 g, 0.0478 Moles). To this mixture was added via dropping funnel over 45 minutes N-ethyl-N-propargylaniline (9.24 g, 0.0581 Moles) in 150 mL DMF. Oxygen was then allowed to bubble through the mixture while stirring. After 21 hours 100 mL of water to which 5 mL of concentrated Hydrochloric acid had been added was added to the reaction mixture dropwise. Then 500 mL of water was added in the same way. This mixture was filtered by suction and washed with a little Hydrochloric acid of the same dilution as previously and dried in a vacuum dissector to yield 5.67 g of light plates (62% yield). Separation on a silica column eluted with a 4:1 Hexane/Ethyl acetate mixture and evaporating to a small volume yielded a product of higher purity, M.P. 109.3-111.4; IR (KBR) 3064, 3029, 2975, 2878, 1599, 1505, 1427, 1385, 1327, 1248, 1185, 749, 693 cm-1 ; 1H NMR (CDCl3) δ1.25 (t, J=7.6), 3.46 (q, J=7.4), 4.11(s, 4), 7.05 (m, 4), 7.31 (d, 4); 13C NMR (CDCl3) δ13.0 (--CH3), 40.1 (N--CH2 --), 46.0 (N--CH2 --), 68.5 (yneC-), 75.4 (yneC--Cyne), 114.3 (arom), 118.3 (arom), 129.7 (arom), 148.2 (arom).

Workup

  1. additionTo this mixture was added
  2. customover 45 minutes
  3. customto bubble through the mixture
  4. additionAfter 21 hours 100 mL of water to which 5 mL of concentrated Hydrochloric acid had been added
  5. additionwas added to the reaction mixture dropwise
  6. additionThen 500 mL of water was added in the same way
  7. filtrationThis mixture was filtered by suction
  8. washwashed with a little Hydrochloric acid of the same dilution as previously and
  9. customdried in a vacuum dissector
  10. customto yield 5.67 g of light plates (62% yield)
  11. customSeparation on a silica column
  12. washeluted with a 4:1 Hexane/Ethyl acetate mixture
  13. customevaporating to a small volume
  14. customyielded a product of higher purity, M.P. 109.3-111.4

Sources & evidence

ORD record
ord-1c04c4cacdc04cd7adc6c9e9cb2e5f87
Source dataset
uspto-grants-1999_12
Patent number
US06005058

Reaction notes

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